EP0817712B1 - Two-step process for producing solid surface material with foam backing - Google Patents

Two-step process for producing solid surface material with foam backing Download PDF

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Publication number
EP0817712B1
EP0817712B1 EP96910548A EP96910548A EP0817712B1 EP 0817712 B1 EP0817712 B1 EP 0817712B1 EP 96910548 A EP96910548 A EP 96910548A EP 96910548 A EP96910548 A EP 96910548A EP 0817712 B1 EP0817712 B1 EP 0817712B1
Authority
EP
European Patent Office
Prior art keywords
mix
filler
layer
article
matrix
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96910548A
Other languages
German (de)
French (fr)
Other versions
EP0817712A1 (en
Inventor
Donald Eugene Swarts
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0817712A1 publication Critical patent/EP0817712A1/en
Application granted granted Critical
Publication of EP0817712B1 publication Critical patent/EP0817712B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C39/12—Making multilayered or multicoloured articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/22—Making multilayered or multicoloured articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B32B5/20—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material foamed in situ
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/06—Acrylates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/00405—Materials with a gradually increasing or decreasing concentration of ingredients or property from one layer to another
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00612—Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate

Definitions

  • This invention relates to a process of producing a composite cast article having a polymeric solid surface with added filler and a backing of similar material also filled with hollow bubbles, with no transition zone of unfilled polymer between the layers.
  • Solid surface materials are known in the art including those based on polymethyl methacrylate and alumina trihydrate. Basic technology for these products is disclosed in U.S. Patents 3,847,865 - Duggins (1974), 4,085,246 - Buser, Roedel and Vassiliou (1978), and published PCT patent application WO 89/05310 - Frank, Otremba, Pohl and Schlier.
  • the present invention provides a process of producing the cast composite article comprising a polymer matrix and two zones of different filler, said article being substantially flat with two opposing faces; a first zone of such article including one face of the article having filler at a level in the range of 10 to 80% by weight of the filler plus matrix, and a second zone including the second face opposing said first face having filler of 5 to 60% and 3 to 30% of bubbles, both by weight of the filler and bubbles plus matrix, said first and second zones forming a continuum with essentially no layer of unfilled matrix between the two zones.
  • Said process comprising the steps of forming a multi-layer composite article by casting on a flat surface a first mix comprising the polymerizable monomer(s) and a filler which will cure to give the composition of said first zone, and, before said first mix cures substantially, casting on the first mix a second mix comprising polymerizable monomer(s), filler, and bubbles which will cure to give the composition of said second zone, under conditions that will cause the second mix and the first mix to interpenetrate, so that there is essentially no interface in the matrix and no resulting layer of unfilled polymer, and curing the resulting composite article.
  • a third layer is added to the second layer, having a composition in the limits of the first layer.
  • a hard face can be added by applying it before the first layer with a filler harder than ATH, such as alumina, silica, calcium carbonate, or natural stone material such as granite.
  • a filler harder than ATH such as alumina, silica, calcium carbonate, or natural stone material such as granite.
  • ground particles of filled or unfilled resin can be added to the first layer in accordance with the ground particles taught in US 4,085,246.
  • An advantage of the invention is that it provides a light weight, more economical solid surface material without any transition zone of polymer which could create a zone of brittleness or cause other mechanical difficulties.
  • Mixture (A) consists of a filler, such as alumina trihydrate, dispersed in a liquid phase consisting of a syrup containing approximately 20% polymethylmethacrylate in methyl methacrylate monomer along with an initiator. Additional monomer may be added to adjust the mix viscosity. Colored pigments and/or particles may be added to get a desired color and pattern.
  • Mixture (B) consists of a filler, usually lightweight, such as hollow glass microspheres along with calcium acarbonate, dispersed in a liquid phase consisting of a syrup containing approximately 20% polymethylmethacrylate in methyl methacrylate monomer and an initiator. Additional monomer may be added to adjust casting viscosity.
  • a typical composition for mixture (B) comprises: Wt % Methyl methacrylate 44.0 Syrup 11.0 Alumina trihydrate 37.0 "Scotchlite" K-1 glass bubbles (20-120 ⁇ m, median 70 ⁇ m, sp.gr. 0.125) 8.0 100.0
  • Mixture (A) is evacuated to remove air, then poured into a mold to form a 0.5cm layer in the bottom of the mold.
  • Mixture (B), also evacuated, is then poured on top of the layer from mixture (A) in the mold while it is still wet and uncured, to form a second layer which is 1.4cm thick.
  • the polymerized form of mixture (A) is the face layer and that of mixture (B) is the back foam layer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Structural Engineering (AREA)
  • Laminated Bodies (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

A process of producing solid surface material is provided with a thin layer of filled polymer integrally formed with a backing of bubble-filled polymer, without an interface or transition zone in the polymer mix, using two-step wet-on-wet casting.

Description

BACKGROUND OF THE INVENTION
This invention relates to a process of producing a composite cast article having a polymeric solid surface with added filler and a backing of similar material also filled with hollow bubbles, with no transition zone of unfilled polymer between the layers.
Solid surface materials are known in the art including those based on polymethyl methacrylate and alumina trihydrate. Basic technology for these products is disclosed in U.S. Patents 3,847,865 - Duggins (1974), 4,085,246 - Buser, Roedel and Vassiliou (1978), and published PCT patent application WO 89/05310 - Frank, Otremba, Pohl and Schlier.
Prior attempts to laminate such solid surface materials with bubble-filled backing material and fiberglass-reinforcement have led to expensive multi-step processes and to laminar products which had distinctly different layers with their own properties. Laminar products generally are more prone to delamination and other weaknesses due to the interface under certain conditions than integral products. Among the multi-layer, laminated products of this type is that of EP 285,046 - Schock (1993), and WO 83/03323.
All of the above-mentioned documents teach methods and materials for making solid surface filled polymeric materials. It would be desirable to be able to provide lighter weight sheet material with the surface characteristics of this solid surface material in integral form without laminar transitions between layers, and to be able to prepare such products by less expensive processes.
SUMMARY OF THE INVENTION
The present invention provides a process of producing the cast composite article comprising a polymer matrix and two zones of different filler, said article being substantially flat with two opposing faces; a first zone of such article including one face of the article having filler at a level in the range of 10 to 80% by weight of the filler plus matrix, and a second zone including the second face opposing said first face having filler of 5 to 60% and 3 to 30% of bubbles, both by weight of the filler and bubbles plus matrix, said first and second zones forming a continuum with essentially no layer of unfilled matrix between the two zones. Said process comprising the steps of forming a multi-layer composite article by casting on a flat surface a first mix comprising the polymerizable monomer(s) and a filler which will cure to give the composition of said first zone, and, before said first mix cures substantially, casting on the first mix a second mix comprising polymerizable monomer(s), filler, and bubbles which will cure to give the composition of said second zone, under conditions that will cause the second mix and the first mix to interpenetrate, so that there is essentially no interface in the matrix and no resulting layer of unfilled polymer, and curing the resulting composite article. In other embodiments, a third layer is added to the second layer, having a composition in the limits of the first layer. Also, a hard face can be added by applying it before the first layer with a filler harder than ATH, such as alumina, silica, calcium carbonate, or natural stone material such as granite. Furthermore, ground particles of filled or unfilled resin can be added to the first layer in accordance with the ground particles taught in US 4,085,246.
DETAILED DESCRIPTION
An advantage of the invention is that it provides a light weight, more economical solid surface material without any transition zone of polymer which could create a zone of brittleness or cause other mechanical difficulties.
Parts, proportions and percentages herein are by weight except where indicated otherwise.
"WET-ON-WET" CASTING PROCEDURE
Two mixtures are prepared so they can be cast sequentially, into a mold, one on top of the other. Mixture (A) consists of a filler, such as alumina trihydrate, dispersed in a liquid phase consisting of a syrup containing approximately 20% polymethylmethacrylate in methyl methacrylate monomer along with an initiator. Additional monomer may be added to adjust the mix viscosity. Colored pigments and/or particles may be added to get a desired color and pattern. A typical composition for mixture (A) comprises:
Wt %
Methyl methacrylate 4.0
Syrup 36.0
Alumina trihydrate 42.0
Colored particles (30-150 mesh U.S. Standard Sieve= 100-600µm) 18.0
100.0
Mixture (B) consists of a filler, usually lightweight, such as hollow glass microspheres along with calcium acarbonate, dispersed in a liquid phase consisting of a syrup containing approximately 20% polymethylmethacrylate in methyl methacrylate monomer and an initiator. Additional monomer may be added to adjust casting viscosity. A typical composition for mixture (B) comprises:
Wt %
Methyl methacrylate 44.0
Syrup 11.0
Alumina trihydrate 37.0
"Scotchlite" K-1 glass bubbles (20-120µm, median 70µm, sp.gr. 0.125) 8.0
100.0
Mixture (A) is evacuated to remove air, then poured into a mold to form a 0.5cm layer in the bottom of the mold. Mixture (B), also evacuated, is then poured on top of the layer from mixture (A) in the mold while it is still wet and uncured, to form a second layer which is 1.4cm thick. After the structure has cured, the polymerized form of mixture (A) is the face layer and that of mixture (B) is the back foam layer. Although there appears to be two separate layers there is no interface between them. They are integral, with the polymer matrix continuous throughout the structure.

Claims (4)

  1. A process of producing a cast composite article comprising a polymer matrix and two zones of different filler, said article being substantially flat with two opposing faces, characterized by a first zone of such article including one face of the article having filler at a level in the range of 10 to 80% by weight of the filler plus matrix, and a second zone including the second face opposing said first face having filler of 5 to 60% and 3 to 30% of bubbles, both by weight of the filler and bubbles plus matrix, said first and second zones forming a continuum with essentially no layer of unfilled matrix between the two zones, said process comprising the steps of forming a multi-layer composite article by casting on a flat surface a first mix comprising polymerizable monomer and filler which will cure to give the composition of said first zone, and, before said first mix cures substantially, casting on the first mix a second mix comprising polymerizable monomer, filler, and bubbles which will cure to give the composition of said second zone, under conditions that will cause the second mix and the first mix to interpenetrate, so that there is essentially no interface in the matrix and no resulting layer of unfilled polymer, and curing the resulting composite article.
  2. The process of claim 1 in which a third mix is cast on the second mix, said third mix being within the composition limits of said first mix under conditions that will cause the third mix and second mix to interpenetrate, so there is no interface in the matrix and no resulting layer of unfilled polymer, and curing the resulting three zone composite article.
  3. The process of producing a hard-faced article by applying a base layer of polymerizable monomer with filler harder than alumina trihydrate to a flat surface, then forming a multi-layer composite article on said base layer and curing the resulting composite article in accordance with claim 1.
  4. The process of claim 3 in which the harder filler is selected from the group consisting of alumina, silica, calcium carbonate and natural stone materials.
EP96910548A 1995-03-29 1996-03-26 Two-step process for producing solid surface material with foam backing Expired - Lifetime EP0817712B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US412792 1995-03-29
US08/412,792 US6582636B1 (en) 1995-03-29 1995-03-29 Two-step process for producing solid surface material with foam backing
PCT/US1996/004045 WO1996030183A1 (en) 1995-03-29 1996-03-26 Two-step process for producing solid surface material with foam backing

Publications (2)

Publication Number Publication Date
EP0817712A1 EP0817712A1 (en) 1998-01-14
EP0817712B1 true EP0817712B1 (en) 1998-12-09

Family

ID=23634508

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96910548A Expired - Lifetime EP0817712B1 (en) 1995-03-29 1996-03-26 Two-step process for producing solid surface material with foam backing

Country Status (10)

Country Link
US (1) US6582636B1 (en)
EP (1) EP0817712B1 (en)
JP (1) JP3007162B2 (en)
KR (1) KR100419372B1 (en)
CN (1) CN1061287C (en)
AT (1) ATE174253T1 (en)
AU (1) AU704611B2 (en)
DE (1) DE69601130T2 (en)
TR (1) TR199600258A2 (en)
WO (1) WO1996030183A1 (en)

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Publication number Priority date Publication date Assignee Title
FR2807029A1 (en) * 2000-03-31 2001-10-05 Auxiliaire Du Maitre D Ouvrage SEALING COMPLEX, PREPARATIONS, USES; ORIGINAL BITUMINOUS CONCRETE
CN100566993C (en) * 2004-12-17 2009-12-09 第一毛织株式会社 Has artificial marble of stacked plywood-looking layer and preparation method thereof
EP3892599A1 (en) * 2020-04-06 2021-10-13 Duravit Aktiengesellschaft Sanitary article

Family Cites Families (15)

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Publication number Priority date Publication date Assignee Title
US2136424A (en) * 1937-06-02 1938-11-15 Du Pont Process of polymerization
GB1076167A (en) 1963-05-21 1967-07-19 Mecmax Ltd Improvements in and relating to the manufacture of artificial materials
US3847865A (en) 1972-04-28 1974-11-12 Du Pont Use of alumina trihydrate in a polymethyl methacrylate article
US4085246A (en) 1975-06-18 1978-04-18 E. I. Du Pont De Nemours And Company Simulated granite and its preparation
JPS5282969A (en) * 1975-12-29 1977-07-11 Kousui Kagaku Kougiyou Kk Method of producing foamed synthetic resin
DE3001205C2 (en) * 1980-01-15 1982-12-09 Fa. August Hohnholz, 2000 Hamburg Process for the production of foam from a polymer
DE3124490A1 (en) 1981-06-23 1983-01-05 Imchemie Kunststoff Gmbh, 5632 Wermelskirchen Process for the curing of polymerisable plastics
US4446177A (en) 1982-03-12 1984-05-01 Munoz George L Reinforced plastic product
JPS60223848A (en) * 1984-04-20 1985-11-08 Inax Corp Joint filling resin material for tile
WO1988004322A1 (en) 1986-12-07 1988-06-16 Biscar Jean P Artificial gravity cellular molecular injection
JPH0274577A (en) * 1988-09-08 1990-03-14 Masao Ose Light-weight artificial stone
DE4126024A1 (en) 1991-08-06 1993-02-11 Roehm Gmbh METHOD FOR PRODUCING POLYMERIZED MOLDING PIECES FROM HIGHLY FILLED CAST RESIN WITH COLOR-DIFFERENTIATED SURFACE AREAS
UA41286C2 (en) * 1991-11-07 2001-09-17 Акбар Гехері COMPOSITIONAL MATERIAL FOR COATINGS
DE69226200T2 (en) * 1991-11-07 1999-03-11 Akbar Ghahary MINERAL-LIKE PLASTICS
JP2625069B2 (en) * 1992-10-26 1997-06-25 花王株式会社 Ammonium salt having ester group, method for producing the same, intermediate diamine, and hair treatment agent

Also Published As

Publication number Publication date
JPH10505030A (en) 1998-05-19
KR100419372B1 (en) 2005-08-04
CN1179746A (en) 1998-04-22
ATE174253T1 (en) 1998-12-15
AU5371596A (en) 1996-10-16
CN1061287C (en) 2001-01-31
TR199600258A2 (en) 1996-10-21
KR19980703371A (en) 1998-10-15
WO1996030183A1 (en) 1996-10-03
AU704611B2 (en) 1999-04-29
US6582636B1 (en) 2003-06-24
JP3007162B2 (en) 2000-02-07
DE69601130T2 (en) 1999-07-08
EP0817712A1 (en) 1998-01-14
DE69601130D1 (en) 1999-01-21

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